Infrared identification of the Criegee intermediates syn- and anti-CH₃CHOO, and their distinct conformation-dependent reactivity

Hui-Yu Lin; Yu-Hsuan Huang; Xiaohong Wang; Joel M Bowman; Yoshifumi Nishimura; Henryk A Witek; Yuan-Pern Lee

doi:10.1038/ncomms8012

Infrared identification of the Criegee intermediates syn- and anti-CH₃CHOO, and their distinct conformation-dependent reactivity

Nat Commun. 2015 May 11:6:7012. doi: 10.1038/ncomms8012.

Authors

Hui-Yu Lin¹, Yu-Hsuan Huang¹, Xiaohong Wang², Joel M Bowman², Yoshifumi Nishimura¹, Henryk A Witek¹, Yuan-Pern Lee³

Affiliations

¹ Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30010, Taiwan.
² Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
³ 1] Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30010, Taiwan [2] Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.

Abstract

The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. So far, the mid-infrared spectrum of only the simplest Criegee intermediate CH2OO has been reported. Methyl substitution of CH2OO produces two conformers of CH3CHOO and consequently complicates the infrared spectrum. Here we report the transient infrared spectrum of syn- and anti-CH3CHOO, produced from CH3CHI + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer. Guided and supported by high-level full-dimensional quantum calculations, rotational contours of the four observed bands are simulated successfully and provide definitive identification of both conformers. Furthermore, anti-CH3CHOO shows a reactivity greater than syn-CH3CHOO towards NO/NO2; at the later period of reaction, the spectrum can be simulated with only syn-CH3CHOO. Without NO/NO2, anti-CH3CHOO also decays much faster than syn-CH3CHOO. The direct infrared detection of syn- and anti-CH3CHOO should prove useful for field measurements and laboratory investigations of the Criegee mechanism.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.